US20080076843A1 - Polyurethane foam composition possessing modified silicone surfactants - Google Patents

Polyurethane foam composition possessing modified silicone surfactants Download PDF

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US20080076843A1
US20080076843A1 US11/524,808 US52480806A US2008076843A1 US 20080076843 A1 US20080076843 A1 US 20080076843A1 US 52480806 A US52480806 A US 52480806A US 2008076843 A1 US2008076843 A1 US 2008076843A1
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polyurethane foam
forming composition
polyols
polyol
foam
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Roger Christopher Clark
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Momentive Performance Materials Inc
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General Electric Co
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Priority to US11/524,808 priority Critical patent/US20080076843A1/en
Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CLARK, ROGER CHRISTOPHER
Priority to CA002662621A priority patent/CA2662621A1/en
Priority to EP07838575A priority patent/EP2069416A1/en
Priority to TW096135164A priority patent/TW200831552A/zh
Priority to CNA2007800352210A priority patent/CN101516949A/zh
Priority to JP2009529239A priority patent/JP2010504399A/ja
Priority to BRPI0718464-6A priority patent/BRPI0718464A2/pt
Priority to PCT/US2007/020390 priority patent/WO2008036365A1/en
Assigned to MOMENTIVE PERFORMANCE MATERIALS INC. reassignment MOMENTIVE PERFORMANCE MATERIALS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GENERAL ELECTRIC COMPANY
Publication of US20080076843A1 publication Critical patent/US20080076843A1/en
Assigned to THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS COLLATERAL TRUSTEE reassignment THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS COLLATERAL TRUSTEE SECURITY AGREEMENT Assignors: JUNIPER BOND HOLDINGS I LLC, JUNIPER BOND HOLDINGS II LLC, JUNIPER BOND HOLDINGS III LLC, JUNIPER BOND HOLDINGS IV LLC, MOMENTIVE PERFORMANCE MATERIALS CHINA SPV INC., MOMENTIVE PERFORMANCE MATERIALS QUARTZ, INC., MOMENTIVE PERFORMANCE MATERIALS SOUTH AMERICA INC., MOMENTIVE PERFORMANCE MATERIALS USA INC., MOMENTIVE PERFORMANCE MATERIALS WORLDWIDE INC., MOMENTIVE PERFORMANCE MATERIALS, INC., MPM SILICONES, LLC
Assigned to MOMENTIVE PERFORMANCE MATERIALS INC. reassignment MOMENTIVE PERFORMANCE MATERIALS INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS COLLATERAL AGENT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • This invention generally relates to a polyurethane foam-forming composition, and in particular to polyurethane form-forming composition possessing modified silicone surfactants and having delayed catalysis.
  • Polyurethane foams are produced by reacting a di- or polyisocyanate with compounds containing two or more active hydrogens, generally in the presence of catalysts, silicone-based surfactants and other auxiliary agents.
  • the active hydrogen-containing compounds are typically polyols, primary and secondary polyamines, and water. Two major reactions are promoted by the catalysts among the reactants during the preparation of a polyurethane foam. These reactions must proceed simultaneously and at a competitively balanced rate during the process in order to yield a polyurethane foam with desired physical characteristics.
  • Reaction between the isocyanate and the polyol or polyamine leads to the formation of a polymer of high molecular weight. This reaction is predominant in foams blown exclusively with low boiling point organic compounds. The progress of this reaction increases the viscosity of the mixture and generally contributes to crosslink formation with polyfunctional polyols.
  • the second major reaction occurs between isocyanate and water. This reaction adds to urethane polymer growth, and is important for producing carbon dioxide gas which promotes foaming. As a result, this reaction often is referred to as the blow reaction.
  • the blow reaction is essential for avoiding or reducing the use of auxiliary blowing agents.
  • the gel and blow reactions must proceed simultaneously and at optimum balanced rates. For example, if the carbon dioxide evolution is too rapid in comparison with the gel reaction, the foam tends to collapse. Alternatively, if the gel extension reaction is too rapid in comparison with the blow reaction generating carbon dioxide, foam rise will be restricted, resulting in a high-density foam. Also, poorly balanced crosslinking reactions will adversely impact foam stability. It is also important that there not be densification at the bottom of the foam.
  • Some of the limitations of the aforementioned amines include delayed activity within the reaction until the salt is dissociated by the increasing temperature of the reacting mixture, their tightening effect on foam compositions, and inability to produce superior lower density grade TDI molded foam.
  • the present invention is based on the discovery that silicone copolymers containing organic acids can complex with the amine catalyst(s), thus delaying the ability of the amine to promote the urethane (gel) and/or the urea (blow) reactions of a polyurethane foam-forming composition.
  • the present invention pertains to a polyurethane foam-forming composition comprising:
  • the silicone surfactants of the present invention can affect the reactivity of a polyurethane system to provide for better flow, openness and processing latitude in molded systems.
  • the silicone surfactants of the present invention provide for improved flow, cavity filling and thermal performance and/or dimensional stability.
  • FIG. 1 is a graphical representation of the temperature profile of Comparative Example 1 and Examples 1 and 2.
  • FIG. 2 is a graphical representation of the rise profile of Comparative Example 1 and Examples 1 and 2.
  • FIG. 3 is a graphical representation of the rise profile of Comparative Example 3 and Example 6.
  • FIG. 4 is a graphical representation of the temperature profile of Comparative Example 3 and Example 6.
  • Polyols containing reactive hydrogen atoms generally employed in the production of polyurethane foams may be employed in the formulations of the present invention.
  • the polyols are hydroxy-functional chemicals or polymers covering a wide range of compositions of varying molecular weights and hydroxy functionality. These polyhydroxyl compounds are generally mixtures of several components although pure polyhydroxyl compounds, i.e. individual compounds, may in principle be used.
  • the present invention is directed to polyurethane foam produced from polyurethane foam-forming composition
  • polyol (a) which is defined herein to be a normally liquid polymer possessing hydroxyl groups.
  • the polyol can be at least one of the type generally used to prepare polyurethane foams, e.g., a polyether polyol (a) having a molecular weight of from about 18 to about 10,000.
  • polyol includes linear and branched polyethers (having ether linkages), polyesters and blends thereof, and comprising at least two hydroxyl groups.
  • Suitable polyols include polyether polyol, polyester polyol, polyetherester polyols, polyesterether polyols, polybutadiene polyols, acrylic component-added polyols, acrylic component-dispersed polyols, styrene-added polyols, styrene-dispersed polyols, vinyl-added polyols, vinyl-dispersed polyols, urea-dispersed polyols, and polycarbonate polyols, polyoxypropylene polyether polyol, mixed poly (oxyethylene/oxypropylene)polyether polyol, polybutadienediols, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycols, polycaprolactone diols and triols, and the like, all of which possess at least two primary hydroxyl groups.
  • polyether polyol (a) are polyoxyalkylene polyol, particularly linear and branched poly(oxyethylene)glycol, poly(oxypropylene)glycol, copolymers of the same and combinations thereof.
  • Graft or modified polyether polyols typically called polymer polyols, are those polyether polyols having at least one polymer of ethylenically unsaturated monomers dispersed therein.
  • Non-limiting representative modified polyether polyols include polyoxypropylene polyether polyol into which is dispersed poly(styrene acrylonitrile) or polyurea, and poly(oxyethylene/oxypropylene)polyether polyols into which is dispersed poly(styrene acrylonitrile) or polyurea. Graft or modified polyether polyols comprise dispersed polymeric solids.
  • Suitable polyesters of the present invention include but are not limited to aromatic polyester polyols such as those made with pthallic anhydride (PA), dimethlyterapthalate (DMT) polyethyleneterapthalate (PET) and aliphatic polyesters, and the like.
  • the polyether polyol (a) is selected from the group consisting of ARCOL® polyol U-1000, Hyperlite® E-848 from Bayer A G, Voranol® Dow BASF, Stepanpol® from Stepan, Terate® from Invista and combinations thereof.
  • Non-limiting examples of suitable polyols (a) are those derived from propylene oxide and ethylene oxide and an organic initiator or mixture of initiators of alkylene oxide polymerization and combinations thereof.
  • the hydroxyl number of a polyol is the number of milligrams of potassium hydroxide required for the complete hydrolysis of the fully acylated derivative prepared from one gram of polyol.
  • the hydroxyl number is also defined by the following equation, which reflects its relationship with the functionality and molecular weight of polyether polyol (a):
  • the average number of hydroxyl groups in polyether polyol (a) is achieved by control of the functionality of the initiator or mixture of initiators used in producing polyether polyol (a).
  • polyol (a) can have a functionality of from about 2 to about 12, and in another embodiment of the present invention the polyol has a functionality of at least 2. It will be understood by a person skilled in the art that these ranges include all subranges there between.
  • polyurethane foam-forming composition comprises polyether polyol (a) having a hydoxyl number of from about 10 to about 4000.
  • polyether polyol (a) has a hydroxyl number of from about 20 to about 2,000.
  • polyether polyol (a) has a hydoxyl number of from about 30 to about 1,000.
  • polyether polyol (a) has a hydroxyl number of from about 35 to about 800.
  • Polyisocyanate (b) of the present invention include any diisocyanate that is commercially or conventionally used for production of polyurethane foam.
  • the polyisocyanate (b) can be organic compound that comprises at least two isocyanate groups and generally will be any of the known aromatic or aliphatic diisocyanates.
  • polyisocyanates that are useful in the polyurethane foam-forming composition of this invention are organic polyisocyanate compounds that contain at least two isocyanate groups and generally will be any of the known aromatic or aliphatic polyisocyanates.
  • the polyisocyanate (b) can be a hydrocarbon diisocyanate, (e.g.
  • the polyisocyanate (b) can be isomers of the above, such as methylene diphenyl diisocyanate (MDI) and 2,4- and 2,6-toluene diisocyanate (TDI), as well as known triisocyanates and polymethylene poly(phenylene isocyanates) also known as polymeric or crude MDI and combinations thereof.
  • Non-limiting examples of isomers of 2,4- and 2,6-toluene diisocyanate include Mondur® TDI,_Papi 27 MDI and combinations thereof.
  • isocyanates are used, e.g., diisocyanates of MDI type and specifically crude polymeric MDI.
  • the polyisocyanate (b) can be at least one mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate wherein 2,4-toluene diisocyanate is present in an amount of from about 80 to about 85 weight percent of the mixture and wherein 2,6-toluene diisocyanate is present in an amount of from about 20 to about 15 weight percent of the mixture. It will be understood by a person skilled in the art that these ranges include all subranges there between.
  • the amount of polyisocyanate (b) included in polyurethane foam-forming composition relative to the amount of other materials in polyurethane foam-forming composition is described in terms of “Isocyanate Index.”
  • “Isocyanate Index” means the actual amount of polyisocyanate (b) used divided by the theoretically required stoichiometric amount of polyisocyanate (b) required to react with all active hydrogen in polyurethane foam-forming composition multiplied by one hundred (100).
  • the Isocyanate Index in the polyurethane foam-forming composition used in the process herein is of from about 60 to about 300, and in another embodiment, of from about 70 to about 200 and in yet another embodiment, of from about 80 to about 120. It will be understood by a person skilled in the art that these ranges include all subranges there between.
  • Catalyst (c) for the production of the polyurethane foam herein can be a single catalyst or mixture of catalysts such as those commonly used to catalyze the reactions of polyol and water with polyisocyanates to form polyurethane foam. It is common, but not required, to use both an organoamine and an organotin compound for this purpose. Other metal catalysts can be used in place of, or in addition to, organotin compound.
  • Suitable non-limiting examples of polyurethane foam-forming catalysts include (i) tertiary amines such as bis(2,2′-dimethylamino)ethyl ether, trimethylamine, triethylenediamine, 1,8-Diazabicyclo[5.4.0]undec-7-ene, triethylamine, N-methylmorpholine, N,N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N′,N′-tetramethyl-1,3-butanediamine, pentamethyldipropylenetriamine, triethanolamine, triethylenediamine, 2- ⁇ [2-(2-dimethylaminoethoxy)ethyl]methylamino ⁇ ethanol, pyridine oxide, and the like; (iii) strong bases such as alkali and alkaline earth metal hydroxides, alkoxides, phenoxides, and the like; (iii) acid
  • organotin compounds that are dialkyltin salts of carboxylic acids can include the non-limiting examples of dibutyltin diacetate, dibutyltin dilaureate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibuytyltindilaurylmercaptide, dibutyltin-bis(6-methylaminocaproate), and the like, and combinations thereof.
  • trialkyltin hydroxide dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride and combinations thereof.
  • these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide) dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and the like, and combinations thereof.
  • catalyst (c) can be an organotin catalyst selected from the group consisting of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, stannous oleate and combinations thereof.
  • catalyst (c) can be an organoamine catalyst, for example, tertiary amine such as trimethylamine, triethylamine, triethylenediamine, bis(2,2′-dimethylamino)ethyl ether, N-ethylmorpholine, diethylenetriamine, 1,8-Diazabicyclo[5.4.0]undec-7-ene and combinations thereof.
  • catalyst (c) can include mixtures of tertiary amine and glycol, such as Niax® catalyst C-183 (GE), stannous octoate, such as Niax® catalyst D-19 (GE, and combinations thereof.
  • the amine catalysts (c), for the production of flexible slabstock and molded foams include bis(N,N-dimethylaminoethyl)ether and 1,4-diazabicyclo[2.2.2]octane.
  • the amine catalysts for the production of rigid foams, include dimethylcyclohexylamine (DMCHA) and dimethylethanolamine (DMEA) and the like.
  • amine catalysts can include mixtures of tertiary amine and glycol, such as Niax® catalyst C-183, stannous octoate, such as Niax® catalyst D-19 and combinations thereof, all available from GE Advanced Materials, Silicones.
  • the at least one silicone possessing carboxylic acid functionality (d) of the present invention possesses a polymeric backbone including repeating siloxy units that have alkyl, aryl, polyether, polyester pendant groups with at least one carboxylic acid (COOH) functionality.
  • the amine catalyst-delaying silicone (d) of the present invention is particularly suitable as a surfactant in the polyurethane foam-forming compositions.
  • the silicone (d) maintain its mobility in the initial stages of the polyurethane foam-forming composition reaction by complexing with the amine catalyst(s) to delay the rise and temperature of the polyurethane foam, stabilize the growth and size of cells within the foam and finally react into the polymer matrix by reacting with the isocyanate to remain in the polymer matrix.
  • silicone surfactants of the present invention can contain one or more acid groups and can be used in conjunction with other silicone surfactants to control the amount of delay.
  • Silicone (d) can be used with any typical amine catalyst in polyurethane foams, and optionally, in combination with metal catalysts such as potassium and tin complexes.
  • silicone surfactants are prepared by reacting a polyhydridosiloxane of general formula M**D, D′ y M** with an appropriately chosen blend of allyl-started oxyalkylene polymers in the presence of a hydrosilation catalyst, e.g., chloroplatinic acid.
  • M** is (CH 3 )(H)SiO 1/2 or (CH 3 ) 3 SiO 1/2
  • D is (CH 3 ) 2 SiO 2/2
  • D′ represents (CH 3 )(H)SiO 2/2 .
  • the allyl-started oxyalkylene polymers are polyethers having a terminal vinyl group, which may optionally be 2-substituted, and containing multiple units derived from ethylene oxide, propylene oxide, or both.
  • the reagents are mixed, generally in a solvent such as toluene or dipropylene glycol, heated to about 70°-85° C., then the catalyst is added, a temperature rise of about 10-15° C. is observed, and the mixture is finally sampled and analyzed for SiH groups by adding an alcohol and base and measuring evolved hydrogen. If a volatile solvent was used, this is removed under vacuum, and the mixture is generally neutralized with a weak base such as NaHCO 3 , then filtered.
  • a solvent such as toluene or dipropylene glycol
  • the polyhydridosiloxanes of the general formula M**D x D′ y M** are prepared in the manner known to the art.
  • M** is (CH 3 ) 3 SiO 1 /2
  • an alkyldisiloxane such as hexamethyldisiloxane
  • a polyhydridosiloxane polymer such as a polyhydridosiloxane polymer
  • an alkyl cyclosiloxane such as octamethylcyclotetrasiloxane
  • a hydridoalkyldisiloxane such as dihydridotetramethyldisiloxane, a polyhydridosiloxane polymer, and an alkyl cyclosiloxane such as octamethylcyclotetrasiloxane are reacted in the presence of a strong acid such as sulfuric acid.
  • allyl-started oxyalkylene polymers also referred to as polyethers
  • polyethers are likewise prepared in the manner known to the art.
  • An allyl alcohol optionally bearing a substituent on the 1 or 2-position, is combined with ethylene oxide, propylene oxide, or both, in the presence of an acid or a base, to yield the desired polyether with a terminal hydroxyl group.
  • This is typically capped by further reaction with an alkylating or acylating agent such as a methyl halide or acetic anhydride, respectively.
  • alkylating or acylating agent such as a methyl halide or acetic anhydride, respectively.
  • Other end caps may of course be employed.
  • Carboxy-functional silicones and methods for preparing them are known in the art, for example, U.S. Pat. Nos. 3,182,076 and 3,629,165, (both to Holdstock) and RE 34,415. The entire contents of the foregoing U.S. patent documents are incorporated by reference herein.
  • carboxy-functional silicones are prepared by the hydrolysis and condensation of a mixture containing organotrichlorosilane, a diorganodichlorosilane, and a cyanoalkyldiorganochlorosilane. During the hydrolysis and condensation of these reactants, the various silicon-bonded chlorine atoms are replaced by silicon-bonded hydroxyl groups which intercondense to form siloxane linkages. The nitrile radical hydrolyzes to a carboxyl radical. Hydrochloric acid is also formed in the hydrolysis reaction.
  • Silicone (d) also can be obtained by reacting a mixture of ingredients containing an olefin-terminated organoacyloxysilane, an organohydrogenpolysiloxane, and a precious metal or a precious metal-containing catalyst and then hydrolyzing the reaction product formed in the first step to form the final product, i.e., the carboxy functional silicone.
  • Another synthetic route for the production of a carboxylic acid adduct consists of reacting an unsaturated acid such as 10-undecenoic acid with trimethylchlorosilane to form the silyl ester followed by a catalytic hydrosilation. A subsequent hydrolysis of the hydrosilated trimethylchlorosilylester of unsaturated acid will yield the siloxy carboxylic acid derivative, as taught in U.S. Pat. No. 4,990,643, which is herewith incorporated by reference.
  • Another method of preparing silicone containing carboxylic acids is summarized by the reaction of an unsaturated polyether with a siloxane containing silicon hydride to form a silicon carbinol or polyether silicone that can be subsequently reacted with an acid anhydride or acid halide to yield a carboxylic acid functionalized silicone or siloxane derivative. This process is described by Raleigh et al. in U.S. Pat. No.
  • the silicone surfactant must contain at least one pendant acid group that can be derived from various methods including direct hydrosilation of acid containing groups or the derivatization of acid groups through various reaction mechanisms including the reaction of hydroxyls with anhydrides such as, e.g., phthalic anhydride, maleic anhydride, succinic anhydride in typical molar ratios as disclosed in U.S. Pat. No. 6,432,864, the entire contents of which are incorporated herein by reference.
  • anhydrides such as, e.g., phthalic anhydride, maleic anhydride, succinic anhydride in typical molar ratios as disclosed in U.S. Pat. No. 6,432,864, the entire contents of which are incorporated herein by reference.
  • the silicone (d) component is a silicone polymer of the general formula MDx D′′y M*z having pendant groups that contains at least one organic acid designated as RCOOH.
  • x is 0 to about 80 and y is of from about 0 to about 25 and z is 0 to 2. In another embodiment of the invention, x is of from about 0 to about 60 and y is of from about 0 to about 20 and z is 0 to 2, and in yet another embodiment of the present invention, x is of from about 0 to about 25 and y is of from about 0 to about 10 and z is 0 to 2.
  • length of silicone backbone can be altered to provide polyurethane foam properties.
  • x can be of from about 0 to about 30 and y+z can be of from about 0 to about 4.
  • x can be of from about 4 to about 8 and y+z can be of from about 0 to about 2. It will be understood by a person skilled in the art that these ranges include all subranges there between.
  • the quantity of silicone surfactant possessing carboxylic acid functionality (d) used in the present invention is typical for silicone surfactants. However, depending on the amount of amine catalysts used and amount of delay that may be required the concentration of the acid functionalized silicones can vary. It is also contemplated herein, that the acid functionalized silicone surfactants can be used in conjunction with unfunctionalized silicone surfactants to obtain the desired effect. The amount used could vary greatly depending on the needs of the cell stabilization and reactivity.
  • the acid functionalized silicone surfactant (d) ranges in amount from about 0.001 to about 10 weight percent of the total foam composition. In another embodiment of the invention, the silicone component (d) ranges in amount from about 0.005 to about 2 weight percent of the total foam composition.
  • the blowing agent of the polyurethane foam-forming composition is water, which is employed to generate carbon dioxide in situ.
  • Physical blowing agents such as, for example, blowing agents based on volatile hydrocarbons or halogenated hydrocarbons and other non-reacting gases can also be used in the polyurethane foam-forming composition.
  • the blowing agents can be used as auxiliary blowing agents, e.g., carbon dioxide and dichloromethane (methylene chloride).
  • blowing agents for use in the polyurethane foam-forming composition include fluorocarbons, e.g., chlorofluorocarbon (CFC), dichlorodifluoromethane, and trichloromonofluoromethane (CFC-11) or non-fluorinated organic blowing agents, e.g., pentane and acetone.
  • fluorocarbons e.g., chlorofluorocarbon (CFC), dichlorodifluoromethane, and trichloromonofluoromethane (CFC-11)
  • non-fluorinated organic blowing agents e.g., pentane and acetone.
  • the quantity of blowing agent varies according to the desired foam density and foam hardness as recognized by those skilled in the art.
  • the amount of hydrocarbon-type blowing agent varies from, e.g., a trace amount up to about 50 parts per hundred parts of polyol (phpp) and CO 2 varies from, e.g., about 1 to about 10%.
  • the polyurethane foam-forming composition can comprise optional components, such as, catalysts, crosslinkers, surfactants, fire retardant, stabilizer, coloring agent, filler, anti-bacterial agent, extender oil, anti-static agent, solvent and mixtures thereof.
  • optional components such as, catalysts, crosslinkers, surfactants, fire retardant, stabilizer, coloring agent, filler, anti-bacterial agent, extender oil, anti-static agent, solvent and mixtures thereof.
  • the optional components include catalysts typically used to catalyze reaction of polyol with diisocyanate. It is common to use both an amine, metal salt, triazine and or a quaternary ammonium salt that produces isocyanurate moieties along with urethane linkages. Trimerization catalysts useful in the present invention can be selected from conventional polyisocyanate-trimerization catalysts.
  • the trimerization catalyst may be alkali salts of aliphatic, cycloaliphatic and aromatic carboxylic acids, for example, potassium acetate, potassium formate and potassium propionate, 2,4,6-tris(dimethylaminomethyl)phenol, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine and diaza-bis-cycloalkene, and the like and mixtures thereof.
  • alkali salts of aliphatic, cycloaliphatic and aromatic carboxylic acids for example, potassium acetate, potassium formate and potassium propionate, 2,4,6-tris(dimethylaminomethyl)phenol, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine and diaza-bis-cycloalkene, and the like and mixtures thereof.
  • Suitable optional crosslinkers of the present invention include compounds having one or more leaving groups (i.e., groups that can be easily hydrolyzed), for example, alkoxy, acetoxy, acetamido, ketoxime, benzamido and aminoxy.
  • Some of the useful crosslinkers of the present invention include alkylsilicate crosslinkers, tetra-N-propylsilicate (NPS), tetraethylorthosilicate, methytrimethoxysilane and similar alkyl substituted alkoxysilane compositions, methyltriacetoxysilane, dibutoxydiacetoxysilane, methylisopropoxydiacetoxysilane, methyloximinosilane and the like.
  • NPS tetra-N-propylsilicate
  • tetraethylorthosilicate methytrimethoxysilane and similar alkyl substituted alkoxysilane compositions
  • methyltriacetoxysilane dibutoxydiacetoxysilane
  • methylisopropoxydiacetoxysilane methyloximinosilane and the like.
  • the level of incorporation of the crosslinker ranges from about 0.01 weight percent to about 20 weight percent, in one embodiment, and from about 0 . 3 weight percent to about 5 weight percent and from about 0.5 weight percent to about 1.5 weight percent of the total composition in another embodiment.
  • Optional surfactants include polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide (EO) and propylene oxide (PO) and copolymers of silicones and polyethers (silicone polyether copolymers), copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an amount ranging from 0 weight percent to about 20 weight percent, more preferably from about 0.1 weight percent to about 5 weight percent, and most preferably from about 0.2 weight percent to about 1 weight percent of the total composition.
  • silicone polyether as a non-ionic surfactant is described in U.S. Pat. No. 5,744,703 the teachings of which are herewith and hereby specifically incorporated by reference.
  • additives may be added to polyurethane foam to impart specific properties to polyurethane foam, as known in the art, including, but not limited to, fire retardant, stabilizer, coloring agent, filler, anti-bacterial agent, extender oil, anti-static agent, solvent and combinations thereof.
  • the polyurethane foam-forming composition of the present invention has a density of from about 5 to about 100 kilograms per meter 3 . In another embodiment of the invention the polyurethane foam-forming composition has a density from about 20 to about 75 kilograms per meter 3 . In still another embodiment of the present invention the polyurethane foam-forming has a density from about 25 to about 45 kilograms per meter 3 .
  • Methods for producing polyurethane foam from the polyurethane foam-forming composition of the present invention are not particularly limited. Various methods commonly used in the art may be employed. For example, various methods described in “Polyurethane Resin Handbook,” by Keiji Iwata, Nikkan Kogyo Shinbun, Ltd., 1987 may be used.
  • the composition of the present invention can be prepared by combining the polyols, amine catalyst, surfactants, and additional compounds including optional ingredients into a premix. This polyol blend is added to the isocyanate. Finally an acceptable blowing agent is introduced to the mixture to aid in forming the cell structure of the foam.
  • a process of preparing polyurethane foam which comprises the steps of: (1) preparing at least one mixture of polyurethane foam-forming composition comprising: (a) at least one polyol; (b) at least one polyisocyanate; (c) at least one amine catalyst for the polyurethane foam-forming reaction; (d) at least one silicone having carboxylic acid functionality, and (e) at least one blowing agent.
  • a polyurethane foam is prepared by the process as described herein.
  • Flexible slabstock foams are usually produced by mixing the reactants generally at an ambient temperature of between about 20° C. and 40° C.
  • the conveyor on which the foam rises and cures is essentially at ambient temperature, which temperature can vary significantly depending on the geographical area where the foam is made and the time of year.
  • Flexible molded foams usually are produced by mixing the reactants at temperatures between about 20° C. and 30° C., and more often between about 20° C. and 25° C.
  • the mixed starting materials are fed into a mold typically by pouring.
  • the mold preferably is heated to a temperature between about 20° C. and 70° C., and more often between about 40° C.
  • the process used for the production of flexible slabstock foams, molded foams, and rigid foams is the “one-shot” process where the starting materials are mixed and reacted in one step.
  • the silicone surfactants of the present invention can also be used in viscoelastic polyurethane foam.
  • Viscoelastic polyurethane foam also known as “dead” foam, “slow recovery” foam, or “high damping” foam, is characterized by slow, gradual recovery from compression. While most of the physical properties of viscoelastic polyurethane foams resemble those of conventional foams, the density gradient of viscoelastic polyurethane foam is much poorer.
  • Suitable applications for viscoelastic polyurethane foam take advantage of its shape conforming, energy attenuating, and sound damping characteristics. Specific applications determine the desired density of the viscoelastic polyurethane foam.
  • Polyol used in viscoelastic polyurethane foam is characterized by high hydroxyl number (OH) and tends to produce shorter chain polyurethane blocks with a glass transition temperature of resulting foam closer to room temperature.
  • Viscoelastic polyurethane foam produced by viscoelastic polyurethane foam-forming composition can have various physical parameters dependant on specific components used. A person skilled in the art can vary specific components based upon desired properties of viscoelastic polyurethane foam and intended use of viscoelastic polyurethane foam.
  • a typical high resilience (HR) flexible foam formulation (as displayed in Table 1) was used to prepare the polyurethane foams of Comparative Example 1 and Examples 1 and 2, by known and conventional means.
  • Acid functional silicones surfactants i.e., Examples 1 and 2) of the general formula M′D y M′ were hydrosilated with organic acids and hydroxyl containing pendant groups and compared in free rise and urethane systems.
  • Rise and temperature profiles of Comparative Example 1 and Examples 1 and 2 were measured and the results are displayed in FIGS. 1 and 2 .
  • the rise and temperature profiles show that organic acid pendant silicones surfactants significantly delayed the reactivity of the rising foams at equal use levels. This delay is shown in the retardation of the temperature and height of the foam.
  • Example 1 Example 2 Hyperlite ® E-848 90 pphp 90 pphp 90 pphp Hyperlite ® E-850 10 pphp 10 pphp 10 pphp Water 3.75 pphp 3.75 pphp 3.75 pphp DEOA-LF 1.65 pphp 1.65 pphp 1.65 pphp Niax ® A-1 0.2 pphp 0.2 pphp 0.2 pphp Niax ® A-33 0.33 pphp 0.33 pphp 0.33 pphp n-Propanol, 3,3′- 1.5 pphp (1,1,3,3,5,5,7,7,9,9,11,11- dodecamethyl-1,11- hexasiloxanediyl)bis- (Surfactant Allyl Alcohol) Undecanoic Acid, 3,3′- 1.5 pphp (1,1,3,3,5,5,7,7,9,9,11,11- dodecamethyl-1,11- hexasiloxanediyl
  • Comparative Example 2 and Examples 3-5 were prepared using the HR polyurethane foam formulation presented in Table 1 and the silicone surfactants displayed in Table 2, respectively.
  • the HR polyurethane foams were prepared by known and conventional means.
  • Exit test time data was measured using a typical isothermal test at 160° F. and mold measuring 15′′ ⁇ 15′′ ⁇ 4′′ as the foam exited the isothermal mold.
  • the exit time from vents on the top of the mold indicate that Examples 3-5, prepared with alkyl acid pendant surfactants, retard the reactivity of the polyurethane foam, significantly.
  • the Exit Time results as measured in seconds are presented in Table 2.
  • the control of reactivity is also a desirable effect in the processing of rigid urethane foams for insulation.
  • the delay of the reactivity can improve flow in intricate parts.
  • Typical blowing agents include water, hydrochlorofluorcarbons, fluorocarbons, methyl formate and various blends of hydrocarbons.
  • Comparative Example 3 contained surfactant R1 which has a hydroxyl functional polyether pendant on a silicone backbone of the general structure of MD x D′ y M and was prepared as follows: In a round 500 ml 4 neck round bottom flask the following component were charged: 187.64 g of (CH 2 ) 2 —CH 3 —O—(C 2 H 4 O) 12—(C 3 H 6 O)—OH, 112.54 g of silanic fluid MD 20 D′ 3 M, and 0.06 g an amine buffer. The 4-neck flask was equipped with a thermocouple, and a nitrogen purge. Material was the agitated at approximately 250 rpm and heated to 85° C.
  • Example 6 was prepared with surfactant R2 which is identical to surfactant R1 except for the modification of the hydroxyl group by reacting with maleic anhydride at a 1:1 molar ratio to form carboxylic acid end groups.
  • R2 was prepared as follows: 10 g of R1 from the procedure described above and 7.7 grams of Maleic anhydride and charging into a 500 ml round bottom flask equipped with a thermocouple, Nitrogen purge, and a Freidrich condenser. Materials were agitated and heated to 120° C. for 6 hours until there was no visible Maleic Anhydride left in the flask (solids). Material was cooled and collected in a bottle for testing.
  • FIGS. 3 and 4 graphically illustrate the rise and temperature profiles of polyurethane foam Comparative Example 3 and Example 6.
  • Polyurethane foam Example 6 displayed significant delay in rise and temperature as presented in FIGS. 3 and 4 , respectively.
  • Example 6 containing the acid terminated silicone surfactant displayed improved flow, and thermal performance was not affected, see Table 4.
  • the polyurethane foams of Comparative Example 3 and Example 6 displayed similar characteristics of appearance, however, the polyurethane foam of Example 6 exhibited delayed rise and temperature profiles.

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CNA2007800352210A CN101516949A (zh) 2006-09-21 2007-09-20 具有改性有机硅表面活性剂的聚氨酯泡沫材料组合物
EP07838575A EP2069416A1 (en) 2006-09-21 2007-09-20 Polyurethane foam composition possessing modified silicone surfactants
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CA002662621A CA2662621A1 (en) 2006-09-21 2007-09-20 Polyurethane foam composition possessing modified silicone surfactants
JP2009529239A JP2010504399A (ja) 2006-09-21 2007-09-20 修正されたシリコーン界面活性剤を有するポリウレタン発泡体組成物
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US9169368B2 (en) 2013-07-30 2015-10-27 Sabic Global Technologies B.V. Rigid foam and associated article
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US9394443B2 (en) 2011-11-10 2016-07-19 Momentive Performance Materials, Inc. Moisture curable organopolysiloxane composition
US9422394B2 (en) 2013-06-28 2016-08-23 Sabic Global Technologies B.V. Thermoplastic polyurethane and associated method and article
US9493691B2 (en) 2013-03-13 2016-11-15 Momentive Performance Materials Inc. Moisture curable organopolysiloxane compositions
US9523002B2 (en) 2011-12-15 2016-12-20 Momentive Performance Materials Inc. Moisture curable organopolysiloxane compositions
US9527959B2 (en) 2011-12-29 2016-12-27 Momentive Performance Materials Inc. Moisture curable organopolysiloxane composition
US9605113B2 (en) 2013-05-10 2017-03-28 Momentive Performance Materials Inc. Non-metal catalyzed room temperature moisture curable organopolysiloxane compositions
US9663657B2 (en) 2011-12-15 2017-05-30 Momentive Performance Materials Inc. Moisture curable organopolysiloxane compositions
US10933609B2 (en) * 2016-03-31 2021-03-02 The Regents Of The University Of California Composite foam
CN113292695A (zh) * 2021-05-19 2021-08-24 黎明化工研究设计院有限责任公司 一种高表面质量自脱模汽车外饰件材料用聚氨酯组合物及其应用
US20210347989A1 (en) * 2018-10-09 2021-11-11 Dow Global Technologies Llc A rigid polyurethane foam formulation and foam made therefrom
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EP3033377A1 (en) * 2013-08-15 2016-06-22 Dow Global Technologies LLC A process to produce polycarbamate, polycarbamate produced thereby and a coating composition comprising the polycarbamate
WO2015041905A1 (en) * 2013-09-20 2015-03-26 Sabic Global Technologies B.V. Polyurethane foam and associated method and article
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US10933609B2 (en) * 2016-03-31 2021-03-02 The Regents Of The University Of California Composite foam
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CN113292695A (zh) * 2021-05-19 2021-08-24 黎明化工研究设计院有限责任公司 一种高表面质量自脱模汽车外饰件材料用聚氨酯组合物及其应用
CN113831538A (zh) * 2021-11-16 2021-12-24 南京美思德新材料有限公司 有机硅共聚物、其的制备方法、硬质泡沫稳定剂和硬质聚氨酯泡沫
CN115215992A (zh) * 2022-08-30 2022-10-21 廊坊市中油嘉昱防腐技术有限公司 一种耐水解聚氨酯硬质泡沫保温材料及其制备方法

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